WO2016135259A1

WO2016135259A1 - Use of polyether carbonate polyols for producing polyurethane foams with stable colour

Info

Publication number: WO2016135259A1
Application number: PCT/EP2016/054014
Authority: WO
Inventors: Lutz Brassat; Ralf Pohlig; Hans-Georg Pirkl
Original assignee: Covestro Deutschland Ag
Priority date: 2015-02-27
Filing date: 2016-02-25
Publication date: 2016-09-01
Also published as: CA2977869A1; CN107428905A; EP3262090A1; US20180237577A1; JP2018506633A

Abstract

The present invention relates to the use of a component A for producing polyurethane foams with stable colour containing: A1 from ≥ 50 to ≤ 100 parts by weight of at least one polyether carbonate polyol with hydroxy number from ≥ 20 mg KOH/g to ≤ 300 mg KOH/g in accordance with DIN 53240, A2 from ≤ 50 to ≥ 0 parts by weight of at least one polyether polyol with hydroxy number from ≥ 20 mg KOH/g to ≤ 250 mg KOH/g in accordance with DIN 53240, where the polyether polyol is free from carbonate units, A3 from 0.5 to 25 parts by weight, in relation to the sum of the parts by weight of components A1 and A2, of water and/or physical blowing agents, A4 from 0 to 10 parts by weight, in relation to the sum of the parts-by-weight of components A1 and A2, of at least one antioxidant, A5 from 0 to 10 parts by weight, in relation to the sum of the parts by weight of components A1 and A2, of auxiliaries and additives, where all of the parts by weight data for components A1 to A5 have been standardised to give a total of 100 for the parts by weight of A1 + A2 in the composition. The invention also relates to the use of a polyurethane foam thus produced with stable colour for producing furniture cushioning, textile inlays, mattresses, automobile seats, headrests, armrests, sponges, foam sheets for use in automobile parts such as roof linings, door side cladding, seat covers and technical components, and to the use, for producing polyurethane foams with stable colour, of a polyol component comprising from > 50 to < 100 weight percent, in relation to the polyol component, of at least one polyether carbonate polyol A1 with hydroxy number from ≥ 20 mg KOH/g to ≤ 300 mg KOH/g in accordance with DIN 53240.

Description

Use of Polvethercarbonatpolvolen to produce color-stable polyurethane foams

The present invention relates to the use of a Poiyethercarbonatpoiyol-containing polyol component for producing color-stable polyurethane foams.

As is known in the art, polyurethane foams are essentially produced from a polyol component and a polyisocyanate component. As is known, polyether polyols are usually used as the polyol component. Such polyols are readily available commercially in various embodiments in terms of their hydroxyl number or their OH functionality and the molecular weight.

In the case of the polyurethane foams produced from polyether polyols, it may be disadvantageous for certain applications that the foams undergo aging phenomena after their preparation, which visually manifest themselves after only a few months by a noticeable color change. It can also be seen that, with molded components made of polyurethane foam, the color change on existing edges is considerably more pronounced, so that the color change becomes even more noticeable. US 2005/065225 A1 discloses UV-stable polyurethane foams. For this purpose, polyisocyanates are reacted with polycarbonate polyols. Optionally, to improve the flexibility of the foams, a polyether polyol may be used as another polyol component. The polycarbonate polyols are obtained by transesterification of carbonate esters and make from this

Basically a comparatively expensive commodity.

The object of the present invention was to provide a way in which more color-stable polyurethane foams can be produced. In this case, as far as possible, both stable-color polyurethane rigid foams and color-stable flexible polyurethane foams should be made accessible.

This object is achieved by using a component A for producing color-stable Polyurethananschaumsto ffe containing

Al> 50 to <100 parts by weight of at least one polyethercarbonate polyol having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <300 mg KOH / g, A2 <50 to> 0 parts by weight of at least one polyether polyol having a hydroxyl number according to DIN 53240 from> 20 mg KOH / g to <250 mg KOH / g, where the polyether polyol is fr i of carbonate units, A3 0.5 to 25 parts by weight, based on the sum of the parts by weight of the components

AI and A2, water and / or physical blowing agents,

A4 0 to 10 parts by weight, based on the sum of the parts by weight of components AI and A2, of at least one antioxidant,

A5 0 to 10 parts by weight, based on the sum of the parts by weight of components A1 and A2, additives and additives,

wherein all parts by weight of components AI to A5 are normalized so that the sum of parts by weight AI + A2 in the composition 100 results. The invention is based on the finding that when using 50 to 100 parts by weight of a Polyethercarbonatpolyols with a Hydroxyizahl. according to DIN 53240 of> 20 mg KOH / g to

<300 mg KOH / g, a visible improvement in the color stability of polyurethane foam produced therefrom can be achieved in comparison with those foams which contain exclusively polyether polyols without carbonate units. In addition to the improved color stability, the polyurethane foams produced according to the invention also contain relatively high amounts of carbon dioxide, which is advantageous from an environmental point of view.

In this respect, a further object of the present invention is the use of a polyol component comprising> 50 to <100 wt .-% based on the polyol component of at least one polyether carbonate polyol AI having a hydroxyl number according to DI 53240 of> 20 mg KOH / g to <300 mg KOH / g for producing color-stable polyurethane foams. In other words, the polyol component for producing the polyurethane chaumsto ffe consist exclusively of the aforementioned polyether carbonate polyol AI, with the remainder other organic polyols are used than those falling under the definition of the polyether carbonate polyol AI.

In addition, the use according to the invention of polyethercarbonate polyols having a hydroxy number according to DIN 53240 over a range of> 20 mg KOH / g to <300 mg KOH / g makes it possible to adapt the hardness of the foams produced to the respective requirement profile. As a result, on the one hand polyurethane rigid foams as well as flexible polyurethane foams can be produced. By using polyether carbonate polyols having a hydroxy number according to DIN 53240 of> 150 mg KOH / g to

<300 mg KOH / g, even flexible polyurethane foams with viscoeiastic properties can be produced. A viscoelastic polyurethane foam or flexible polyurethane foam is understood as meaning a foam which has a low ball rebound elasticity according to DIN EN ISO 8307: 2007. Thereafter, a ball of defined height is dropped onto a scraper and the height to which the ball jumps up against the direction of fall is measured. The springback height is set in percentage relation to the fall height. A low percentage means a low resiliency. Ideally, the ball does not jump measurably high after the impact, which means that the ball rebound resilience is 0%; in an advantageous embodiment of the method according to the invention, a viscoelastic polyurethane foam or flexible polyurethane foam is obtained which has a ball rebound resilience according to DIN EN ISO 8307: 2007 from 0% to 20%, in particular from 0% to 15%, preferably 0% to 10% or even 0% to 8%. Also preferred are polyurethane foams or flexible polyurethane foams with a ball-rebound resilience according to DIN EN ISO 8307: 2007 of 2% to 20%, in particular from 2% to 15%.

A color-stable polyurethane foam is understood in particular to mean that the color-stable polyurethane foam in the form of a rectangular or square specimen on the center of at least one of its flat sides causes a shift of at least 5 ° in the color angle in the HSI model after storage for a period of 90 days at 20 ° ° C and 40% rel. Humidity as a reference polyurethane foam, which is prepared and stored in the same manner as the color-stable polyurethane foam, wherein the reference polyurethane foam differs from the color-stable polyurethane foam only in that for its preparation instead of the polyethercarbonate polyol AI a largely identical amount of a polyether polyol is used without carbonate units but with largely the same hydroxyl number according to DIN 53240. The rectangular or square specimen should not have a side edge shorter than 0.5 cm, since the aging phenomena are greatest at the edges and thus an evaluation of the color change of the main (pool) is difficult on the center of at least one of its flat sides a shift of the Färb angle in the HSI model by at least 8 ° smaller than the specimen from the reference Poiyurethanschaum on, in particular at least 10 ° or at least 15 ° .. It is understood that the polyurethane foams for these Measurements should not contain any dyes or colored pigments in order not to falsify the measurement All of the above color shift values refer to storage under the above conditions in the dark These values may be even higher when exposed to daylight or under UV irradiation , In the present case, a "smaller shift of the color angle" as a rule means a less pronounced lowering of the color angle from higher grades to lower grades, ie, for example, from greenish hues (angle H = 120 °) to yellowish hues (angle I i = 60 °). ,

The color angle is determined by using a digital camera (Sony DSC-R I) to photograph the respective specimen lying on a white sheet of paper, perform a white balance against the white sheet of paper, and then adjust the hue as the color angle from the HSI model recorded using image analysis software (AnalySIS). The hue is determined as the color angle H on the color wheel (0 ° = red, 120 ° = green, 240 ° = blue) and specifies the dominant wavelength of the color, except for the range between blue-violet and red (240 ° and 360 °). where he gives a position on the purple line. This measurement is carried out in each case with a color-stable polyurethane foam produced according to the invention after the aforementioned aging and a reference polyurethane foam aged in the same way. The determined color angles of the color-stable polyurethane foam and of the reference polyurethane foam are subtracted from one another and thus provide the invention by at least 5 ° lower displacement of the color angle in the color-stable polyurethane foam. As stated above, the color-stable polyurethane foam produced according to the invention and the reference polyurethane foam differ only in that in the reference polyurethane foam a largely identical amount of a Poiyetherpolyois without carbonate units but with the same hydroxyl number according to DIN 53240 instead of the Polyethercarbonatpolyols AI is used. Thus, for example, instead of a polyethercarbonate polyol Al having a hydroxyl number according to DI N 53240 of 150 mg / 'KOH a Polyetherpoiyol having a hydroxyl value according to DIN 53240 of 150 mg / KOH. Conveniently, ten identical samples are measured and the average value is formed.

To prepare the polyurethane foams, the reaction components are reacted according to the known one-step process, often using mechanical equipment, for example those described in EP-A 355 000. Details of processing equipment which also come into question according to the invention, in Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1993, for example, on pages 139 to 265 described. In a preferred embodiment of the use according to the invention, component A with a component B is used for the preparation of the color-stable polyurethane foams

B di- and / or polyisocyanates,

reacted at an isocyanate index of 70 to 130.

The polyurethane foams produced by the process according to the invention can be produced as molds or as slab foams, preferably as bio-cushions. In this respect, a further object of the present invention is the use of the inventive color-stable polyurethane foams for the production of moldings and the moldings themselves.

A particularly preferred polyurethane foam or flexible polyurethane foam, which is obtainable by the process according to the invention, is one for whose preparation a polyether carbonate polyol A 1 having a hydroxyl number according to DIN 53240 of> 250 mg KOH / g to <300 mg KOH / g is used. Such a polyurethane foam or flexible polyurethane foam in addition to the good color stability is characterized by particularly good viscoelastic properties, ie a particularly low ball-rebound resilience according to DIN EN ISO 8307: 2007. In this case, the polyethercarbonate polyol Al used in particular has an average OH functionality of 2.3 to 3.5, in particular from 2.5 to 3.3. preferably from 2.7 to 3.1, more preferably from 2.8 to 3.0.

The indefinite term "a" generally stands for "at least one" in the sense of "one or more." The person skilled in the art understands, depending on the situation, that not the indefinite article but the specific article "a" in the sense of "1" is meant or the indefinite article "a" also includes, in one embodiment, the particular article "a" (1).

The components used in the process according to the invention are described in more detail below. Component AI

Component AI comprises a polyethercarbonate polyol having a hydroxyl number (OH number) according to DI 53240 of> 20 mg KOH / g to <300 mg KOH / g, preferably from> 24 mg KOH / g to <280 mg KOH / g, more preferably from> 40 mg KOH / g to <280 mg KOH / g. Especially for the production of viscoelastic foams, it is preferred that the polyether carbonate polyol AI has a hydroxyl number according to DIN 53240 of> 150 mg KOH / g to <300 mg KOH / g, in particular from> 180 mg KOH / g to <300 mg KOH / g, more preferably from> 250 mg KOH / g to <280 mg KOH / g.

The abovementioned polyether carbonate polyols are obtainable, for example, by copolymerization of> 2% by weight to <30% by weight of carbon dioxide and> 70% by weight to <98% by weight of one or more alkylene oxides, in the presence of one or more H-functional Starter molecules having an average functionality of> 1 to <6, preferably> 1 and <4, more preferably> 2 and <3. Preferably, in the copolymerization> 10 wt .-% to <27 wt .-% carbon dioxide are used, especially preferably> 15% by weight to <25% by weight. For the purposes of the invention, "H-functional" is understood as meaning a starter compound which has active H atoms relative to alkoxylation.As hydroxy-functional starter molecule, it is possible to use, for example, trimethylolpropane, glycerol and / or propylene glycol and / or orbital The copolymerization of carbon dioxide and one or more alkylene oxides preferably takes place in the presence of at least one multimetal cyanide catalyst or double metal cyanide catalyst (DMC catalyst).

Preferably, the polyether carbonate polyols used according to the invention also have ether groups between the carbonate groups, which is shown schematically in formula (I). In the scheme according to formula (I), R stands for an organic radical such as alkyl, alkylaryl or aryl, which may in each case also contain heteroatoms such as, for example, O.S, Si etc., e and f stand for integers. The polyether carbonate polyol shown in the scheme according to formula (I) should only be understood so that blocks with the structure shown can in principle be found in the polyether carbonate polyol, the order, An / ah! and length of the blocks may vary and is not limited to the polyethercarbonate polyol shown in formula (I). With respect to formula (I), this means that the ratio of e / f is preferably from 2: 1 to 1:20, more preferably from 1.5: 1 to 1:10.

The proportion of incorporated CO: ("carbon dioxide-derived units") in a polyether carbonate polyol can be determined from the evaluation of characteristic signals in the Ή-NMR spectrum The following example illustrates the determination of the proportion of Carbon dioxide derived units in a C02 / propylene oxide polyethercarbonate polyol started on 1,8-octanediol.

The proportion of incorporated CO2 in a polyether carbonate polyol and the ratio of propylene carbonate to Polyethercarbonatpolyol can by means of ^! H-NM (a suitable device is to be determined by the Finn Bruker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10s, 64 scans). Each sample is dissolved in deuterated chloroform. The relevant resonances in the 'H-MR (based on TMS = 0 ppm) are as follows: cyclic carbonate (which was formed as a by-product) with resonance at 4.5 ppm; Carbonate resulting from carbon dioxide incorporated in the polyethercarbonate polyol having resonances at 5.1 to 4.8 ppm; unreacted propylene oxide (PO) with resonance at 2.4 ppm; Polyether polyols (ie, with no incorporated carbon dioxide) with resonances at 1.2 to 1.0 ppm; as a starter molecule (if any) built 1.8 octanediol with a resonance at 1.6 to 1 .52 ppm.

The molar fraction of the carbonate incorporated in the polymer in the reaction mixture is calculated according to the formula (II) as follows, using the following abbreviations:

F (4,5) = area of resonance at 4.5 ppm for cyclic carbonate (equivalent to one atom of H) F (5, 1 -4.8) = area of resonance at 5.1 -4.8 ppm for polyethercarbonate polyol and a H atom for cyclic carbonate.

F (2,4) = area of resonance at 2.4 ppm for free, unreacted PO

F (1,2-1,0) = area of resonance at 1, 2-1, 0 ppm for polyether polyols

F (1, 6-1, 52) = area of resonance at 1.6 to 1.52 ppm for 1.8 octanediol (starter), if any.

Taking into account the relative intensities, the following formula (II) for the polymerically bound carbonate ("linear carbonate" LC) in the reaction mixture was converted to mol%:

The weight fraction (in% by weight) of polymer-bound carbonate (LC) in the reaction mixture was calculated according to formula (III)

(III) This gives the value for N ("denominator" N) according to formula (IV) as follows:

N = [F (5.1 ~ 4.8) ~ F (4.5)] * 102 + F (4.5) * 102 + F (2.4) * 58 + 0.33 * F (1, 2 ~ - 1, 0) * 58 + 0.25 * F (1.6 - 1.52) * 146

(IV)

The factor 102 results from the sum of the molecular weights of CO. (Molar mass 44 g / mol) and that of propylene oxide (molar mass 58 g / mol), the factor 58 results from the molecular weight of propylene oxide and the factor 146 results from the Moimasse of the starter used 1, 8-octanediol (if present).

The weight fraction (in% by weight) of cyclic carbonate (CC) in the reaction mixture was calculated according to formula (V),

_CC , ₌ (4,5) * 102 _100%

^N (V) where the value of N is calculated according to formula (IV). From the values of the composition of the reaction mixture, the composition based on the polymer portion (consisting of polyether polyol, soft starter and propylene oxide during the under C0 ₂ -free conditions occurring activation steps has been established, and polyether carbonate polyol, composed of starter, propylene oxide and carbon dioxide during calculated in the presence of CO: activation steps and during the copolymerization), the non-polymer constituents of the reaction mixture (ie cyclic propylene carbonate and possibly present, unreacted propylene oxide) were computationally eliminated. The weight fraction of the carbonate repeat units in the polyethercarbonate polyol was converted to a weight fraction of carbon dioxide by the factor F = 44 / (44 + 58). The indication of the CO content in the polyethercarbonate polyol is normalized to the proportion of the polyethercarbonate polyol molecule formed in the copolymerization and, if appropriate, the activation steps in the presence of CO 2 (ie the proportion of the polyethercarbonate polyol molecule which is known from US Pat Starter (1, 8-octanediol, if any) as well as resulting from the reaction of the initiator with epoxide, which was added under CO.-free conditions, was not considered here).

For example, the preparation of polyethercarbonate polyols according to AI involves:

(a) a Fl-functional starter substance or a mixture of at least two H-functional starter substances are initially charged and optionally water and / or other volatile compounds are removed by elevated temperature and / or reduced pressure ("drying"), the DMC - Catalyst of the H-functional starter substance or the Mixture of at least two H-functional starter substances is added before or after drying,

(ß) for the activation of a partial amount (based on the total amount used in the activation and copolymerization of alkylene oxides) of one or more alkylene oxides to the mixture resulting from step (a) is added, wherein this addition of a partial amount of alkylene oxide, optionally in the presence CO2 can be carried out, and in which case the temperature peak occurring due to the following exothermic chemical reaction ("hotspot") and / or a pressure drop in the reactor is respectively awaited, and wherein the step (β) for activating can also take place several times,

(γ) one or more of the alkylene oxides and carbon dioxide are added to the mixture resulting from step (β), wherein the alkylene oxides used in step (β) may be identical or different from the alkylene oxides used in step (γ).

In general, alkylene oxides (epoxides) having 2 to 24 carbon atoms can be used for the preparation of the polyether carbonate polyols A1. The alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butoxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentoxide, 2,3-pentenoxide, 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 1 -hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl 1, 2-pentenoxide, 4-methyl-1, 2-pentenoxide, 2-ethyl-l, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecene oxide, 1-dodecenoxide, 4-methyl-1, 2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or multiply epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, C i -CM Esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol, such as methyl glycidyl ether, ethyl glycidyl ether,

2-ethylhexyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and epoxy-functional alkoxysilanes, such as, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropylmethyldimethoxysilane,

3-glycidyloxypropylethyldiethoxysilane, 3-glycidyloxypropyltri-isopropoxysilane. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide, particularly preferably propylene oxide.

In a preferred embodiment of the invention, the proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used> 0 and <90 wt .-%, preferably> 0 and <50 wt .-% and particularly preferably free of ethylene oxide. As a suitable H-functional starter substance compounds with active for the alkoxylation H atoms can be used. For the alkoxylation active groups having active H atoms are, for example, -OH, -NH; (primary amines), -NH- (secondary amines), -SH and - CO2H, preferred are -OH and NH:, particularly preferred is -OH. As H-functional starter substance, for example, one or more compounds selected from the group consisting of water, monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, hydroxyesters, polyether polyols, polyester polyols, polyester ether polyols, Polyethercarbonatpolyole, polycarbonate polyols, polycarbonates, polyethyleneimines , polyetheramines (z. B. so-called Jeffamine ^® from Huntsman, such as. for example, D-230, D-400, D-2000, T-403, T-3000, T-5000, or corresponding products from the BASF such. B. polyetheramine D230, D400, D200, T403, T5000), polytetrahydrofurans (z. B. PolyTHF from BASF ^®, such. as PolyTHF ^® 250, 650S, 1000, 1000S, 1400, 1800, 2000), Polytetrahydrofuranamine (BASF Product polytetrahydrofuran amine 1700), polyether thiols, polyacrylate polyols, castor oil, the mono- or digiyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and / or triglycerides of fatty acids, and C1-C24 alkyl-F acid esters containing on average at least 2 OH sip per molecule used. By way of example, it is at the C1-C24 alkyl fatty acid ester sipping on average at least 2 OH-G per molecule to commercial products such as Lupranol Balance ^® (Fa. BASF AG), Merginoi ^® grades (Fa. Hobum Oleochemicals GmbH ) Sovermol ^® grades (Messrs. Cognis Germany GmbH & Co. KG) and Soyol ^® TM types (Fa. USSC Co.).

Polyhydric alcohols suitable as H-functional starter substances are, for example, dihydric alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, bis (hydroxymethyl) - cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols); trihydric alcohols (such as tri methylol propane, glycerol, trishydroxyethyl isocyanurate, castor oil); four-chain alcohols (such as pentaerythritol); Polyalcohols (such as sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, C ellulo sehy droly sate, hydroxy-functionalized fats and oils, in particular castor oil), and all modifying products of these aforementioned alcohols with different amounts of ε-caprolactone. in mixtures of H-functional starters may also be trihydric alcohols. such as trimethylolpropane, glycerol, trishydroxyethyl isocyanurate and castor oil can be used. The H-functional starter substances may also be selected from the class of polyether polyols, in particular those having a molecular weight M _n in the range from 100 to 4000 g / mol, preferably 250 to 2000 g mol. Preference is given to polyether polyols. which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide. Suitable polyether polyols. composed of repeating propylene oxide and / or ethylene oxide units are, for example Desmophen ^® -, Acciaim ^® -, Arcol ^® -, Baycoil ^® -, Bayfill ^® -, Bayflex ^® - Baygal ^® -, PET ^® - and Po 1 yet ago - Po 1 yo 1 e of Bayer MaterialScience AG (such. as Desmophen ^® 3600Z, Desmophen ^® 1900U, Acciaim ^® polyol 2200 Acciaim ^® polyol 40001, Arcol ^® polyol 1 004 Arcol ^® polyol 1010 Arcol ^® polyol 1030 Arcol ^® polyol 1070, Baycoil BD ^® 11 10 Bayfill VPPU ^® 0789, Baygal ^® K55, PET ^® 04 1, polyethers ^® S 180). Other suitable homo- polyethylene oxides are, for example Pluriol ^® E brands from BASF SE, suitable homo- polypropylene oxides are, for example Pluriol ^® P brands from BASF SE, suitable mixed copolymers of ethylene oxide and propylene oxide such as the Pluronic ^® PE or PLURIOL ^® RPE Brands of BASF SE. The II-functional starter substances can also be selected from the substance class of the polyester polyols, in particular those having a molecular weight M _n in the range from 200 to 4500 g mol, preferably from 400 to 2500 g / mol. Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. Succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride,

Hexahydrophthalic anhydride or mixtures of said acids and / or anhydrides used. As alcohol components z. B. ethanediol, 1, 2-propanediol, 1, 3-propanediol. 1 .4-Butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, l, 4-bis (hydroxymethyl) cyclohexane, diethylene glycol. Dipropylene. Trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned. If divalent or polyhydric polyether polyols are used as the alcohol component, polyester polyester polyols which can likewise be used as starter subplants for the preparation of the polyether carbonate polyols are obtained. If polyether polyols are used to prepare the polyester-polyester, polyether polyols having a number-average molecular weight M _{n of} from 150 to 2000 g mol are preferred. Furthermore, polycarbonate polyols (such as, for example, polycarbonate diols) can be used as H-functional starter substances, in particular those having a molecular weight M _n in the range from 150 to 4500 g / mol, preferably 500 to 2500, for example by reaction of phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or polyether polyols. Examples of polycarbonate polyols are found, for. B. in EP-A 1359177. For example, the Desmophen ^® C types of Bayer MaterialScience AG can be used as polycarbonate, such. B. Desmophen ^® C 1100 or Desmophen ^® C 2200th

Likewise, polyether carbonate polyols can be used as H-functional parts Startersub punching. In particular, polyether carbonate polyols prepared by the method described above are used. These polyether carbonate polyols used as H-functional starter substances are previously prepared in a separate reaction step.

Preferred H-functional starter substances are alcohols of the general formula (VI)

HO- <CH: k-OH (VI) where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of alcohols according to formula (V) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol. Further preferred H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols according to formula (V) with ε-caprolactone, for example reaction products of trimethylolpropane with ε-caprolactone, reaction products of glycerol with ε-caprolactone, and reaction products of Pentaerythritol with ε-caprolactone. Preference is furthermore given to using water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyetherpolyols composed of repeating polyalkylene oxide units as the H-functional starting substances. Particularly preferably, the H-functional. Starter substances to one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-methylpropane-l, 3-diol, Neopentyl glycol, 1,6-hexanediol, diethylene glycol. Dipropylengiykoi. Glycerol, trimethylolpropane, di- and tri functional polyether polyols. wherein the polyether polyol is composed of a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide. The polyether polyols have preferably has a number average molecular weight M _n in the range from 62 to 6000 g mol and in particular a number average molecular weight M _n in the range from 350 to 4500 g / mol, very particularly preferably a molecular weight from 500 to 4000 g / mol. The polyether polyols preferably have a functionality of> 2 to <3.

In a preferred embodiment of the invention, the polyethercarbonate polyol Al is obtained by addition of carbon dioxide and alkylene oxides to H-functional starter substances using multimetal cyanide catalysts or double metal cyanide catalysts (DMC catalysts). The preparation of Polyethercarbonatpolyoien by addition of alkylene oxides and CO ₂ to H-functional starter substances using DMC catalysts is known for example from EP-A 0222453, WO-A 2008/013731 and EP-A 2115032.

In principle, DMC catalysts are known from the prior art for the homopolymerization of epoxides (see for example US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922). DMC catalysts which are described, for example, in US Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO-A 97/40086, WO-A 98/16310 and WO-A 00 No. 4,676,409 have very high aldivity in the homopolymerization of epoxides and allow the preparation of polyether polyols and / or polyether carbonate polyols at very low catalyst levels (25 ppm or less). A typical example are the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complexing ligand (eg tert-butanol), also contain a polyether having a number average molecular weight M _n contained as 500 g / mol.

The DMC catalyst is usually in an amount of <1 wt .-%, preferably in an amount of <0.5 wt .-%, more preferably in an amount of <500 ppm and in particular in one

Amount of <300 ppm, in each case based on the weight of the polyether carbonate used. In a preferred embodiment of the invention, the polyether carbonate polyol AI has a

Content of carbonate groups ("carbon dioxide derived units"), calculated as CO2, of

> 2.0 and <30.0 wt .-%, preferably of> 5.0 and <28.0 wt .-%, particularly preferably of

> 10.0 and <26.0 wt .-% and very particularly preferably> 15.0 and <25.0%. In a further embodiment of the invention, the polyether carbonate polyols according to AI have a hydroxyl number of> 20 mg KOH / g to <300 mg KOH / g and are obtainable by copolymerization of> 2.0 wt .-% to <30.0 wt .-% carbon dioxide and> 70 wt .-% to <98 wt .-% of propylene oxide in the presence of a hydroxy-functional starter molecule, such as trimethylolpropane and / or glycerol and / or propylene glycol and / or sorbitol. The hydroxyl number can be determined according to DIN 53240.

According to a further preferred embodiment of the invention, a polyether carbonate polyol Al is used which blocks according to formula (I) having a ratio e / f of 2: 1 to 1: 20, in particular from 1, 5: 1 to 1: 10. In the frame According to the invention, it is preferred that component A contains> 55 to <100 parts by weight of polyethercarbonate polyol A1 and <45 to> 0 parts by weight of polyether polyol A2, in particular> 60 to <100 parts by weight of polyethercarbonate polyol A1 and <40 to

> 0 parts by weight of the polyether polyol A2. In a further embodiment of the invention, component Al is added to 100 parts by weight of T

Component A2 to 0 parts by weight and apart from AI used no further organic polyols.

In the context of the present invention, it is particularly preferred that the polyethercarbonate polyol Al has an average OII functionality of 2.3 to 3.5, in particular from 2.5 to 3.3, preferably from 2.7 to 3.1, especially preferably 2.8 to 3.0.

Component A2

Component A2 comprises Polyetherpoiyole having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g, preferably from> 20 to <1 12 mg KOH / g and more preferably> 20 mg KOH / g to <80 mg KOH / g and is free from carbonate units. The preparation of the compounds according to A2 can be carried out by catalytic addition of one or more alkylene oxides to H-functional starter compounds. As alkylene oxides (epoxides) it is possible to use alkylene oxides having 2 to 24 carbon atoms. The alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butoxide, 2-methyl-1,2-propene oxide (isobutene oxide). , 1-pentenoxide, 2,3-pentenoxide, 2-methyl-1, 2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl 1-2-penteneoxide, 4-methyl-1,2-pentene-2-oxide, 2-ethylbenzene, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1, 2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or poly-epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, O-C24 esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol, such as methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and epoxide functional alkyoxysilanes such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3 -Glycidyloxypropyl-methyl-dimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 3-glycidyloxypropyltri-isopropoxysilane. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. Particularly preferably, an excess of propylene oxide and / or 1, 2-butylene oxide is used. The alkylene oxides can be fed to the reaction mixture individually, in a mixture or in succession. They may be random or block copolymers. If the alkylene oxides are metered in succession, the products produced (polyether polyols) contain polyether chains with block structures.

The H-funldionellen starter compounds have functionalities of> 2 to <6 and are preferably hydroxy-functional (OH-functional). Examples of hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12-dodecanediol , Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1, 3,5-trihydroxybenzene, condensates of formaldehyde and phenol or melamine or urea containing methylol groups. The starter compound used is preferably 1,2-propylene glycol and / or glycerol and / or trimethylolpropane and / or sorbitol.

The polyether polyols according to A2 preferably have a content of> 0 to <40 wt .-%, particularly preferably> 0 to <25 wt .-% of ethylene oxide. Component A3

As component A3, 0.5 to 25 parts by weight, preferably 1.0 to 15 parts by weight, particularly preferably 1.5 to 10 parts by weight, based on the sum of the parts by weight of components AI and A2 , Water and / or physical blowing agents used. As physical blowing agents, for example, carbon dioxide and / or volatile organic substances are used as blowing agents. Preferably, water is used as component A3. Component A4

Antioxidants which can be used in the production of flexible polyurethane foam materials are known per se to the person skilled in the art. Such compounds are described, for example, in EP-A 1874853, G. Oerie! (Ed.): "Kunststoff-Handbuch", Volume VII, Carl Hanser Verlag, Munich, Vienna 1993, Chapter 3.4.8 or in Ullmanns Encyclopedia of Industrial Chemistry Peter P. Klemchuck, 2012, Vol. 162 ff, Wiley VC H-Verlag.

According to a preferred embodiment of the invention, the component A4 comprises an antioxidant A4.1, which is free of compounds with amino groups, and an antioxidant A4.2, which comprises at least one compound having one or more amino groups used.

In a further advantageous embodiment of the invention, the component A4 contains as a component

A4.1 0.02 5.0 parts by wt., Based on the sum of the parts by wt. Of components AI and A2, of an antioxidant which is free of amino groups, and as component A4.2 0.02 5, 0 parts by wt., Based on the sum of the parts by wt. Of components AI and A2, of an antioxidant which comprises at least one compound having one or more amino groups, wherein the total content of component A4 in particular 0.04 - 10.0 wt ., Parts, based on the sum of parts by weight of component AI and A2, is. In the present invention, furthermore, the antioxidant A4.1 and A4.2 may each be contained in an amount of 0.05-1.5 parts by weight, based on the sum of the parts by weight of the components A1 and A2, the total content the component A4 in particular 0.1-3.0 parts by wt., Based on the sum of the parts by weight of component AI and A2, is antioxidants A4.1, which are free of amino groups include compounds containing

i) phenol derivatives

ii) lactones, in particular benzur-2-one derivatives

iii) phosphorus derivatives,

as well as any mixtures of these compounds.

Compounds containing phenol derivatives i) are, for example, 2,6-di- (t-butyl) -p-cresol (BHT), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 2 '2'-Methylenebis (4-methyl-6-t-butylphenol), 2,6-di-tert-butyl-4-metylphenol, Ν, Ν' - 1, 6-hexamethylene-bis-3 - (3,5 -di-t-butyl-4-hydroxyphenyl) propionamide, alkyi-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate) wherein alkyl is a carbon radical having Cl to C24, preferably Cl to C20, more preferably Cl to C18 comprises, ethylene- (bisoxyethylene) bis- (3, (5-t-butylhydroxy-4-tolyl) -propionate 4,4'-butylidenebis (6- t-butyl-3-methylphenol) and / or tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E), preferably 2,6-di- (t-butyl) -p-cresol (BHT), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, alkyl 3 - (3, 5-di-t-butyl-4-hydroxyphenylpropionate), wherein Alkyl comprises a carbon radical having Cl to C24, preferably Cl to C20, particularly preferably Cl to C 18, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate), α-tocopherol, β-tocopherol, γ -Tocopherol and / or δ-tocopherol.

Amine-free lactones ii), in particular benzofuranones, are described, for example, in EP-A 1291384 and DE-A 19618786. Preferred benzofuranones are, for example, 5.7-di-tert-butyl-3-phenyl-benzofuran-2-one, 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) benzofuran-2 on, 5.7-di-t-butyl-3- (2,3-dimethylphenyl) -benzofuran-2-one and / or 5-t-octyl-3- (2-acetyl-5-t-octylphenyl) -benzofirran-2 on.

Antioxidants iii) are, for example, phosphites and phosphonites. These are described, for example, in EP-A 905180 and EP-A 1874853, e.g. Triphenyl phosphite, diphenyl alkyiphosphite, phenyl dialkyl phosphite, tris (nonylphenol) phosphotite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, bisisodecyloxypentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2 , 4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra- t-butyl-12H-dibenzo [d, g] -1,3,3-dioxaphosphocine, 6-fluoro-2,4,8,1-O-tetra-t-butyl-12-methyldibenzo [d, g] -l , 3,2-dioxaphosphocine, bis (2,4-di-t-butyl-6-methylphenyl) methyl phosphite and / or bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite.

Antioxidants A4.2, which comprise at least one compound having one or more amino groups, are generally secondary amines of the formula (VII) H NR 1 R 2 (VII), where R 1 is C 1 -C 18 alkyl, phenylC 1 -C ^' 4-alkyl. C 5-5 2-cycloalkyl. Phenyl, naphthyl, phenyl or naphthyl, each of which is substituted by C1-C12 alkyl or C1-C12 alkoxy or benzyl or α, α-dimethylbenzyl, and R2 is phenyl, naphthyl, phenyl or naphthyl, each of which is substituted by C1 -C12 alkyl or C1-C12 alkoxy or benzyl or α, α-

Dimethylbenzyl corresponds. Suitable antioxidants A4.2 are, for example, N, N'-di-isopropyl-p-phenylenediamine, Ν, Ν'-di-sec-butyl-p-phenylenediamine, N, N'-bis (l, 4-dimethyloentyl) -p -phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, Ν, Ν'-dicyclohexyl-p- phenylenediamine, N, N'-diphenyi-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl ) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -phenyl-p-phenylenediamine, N-cyclohexyl-N-phenyl-p-phenylenediamine, 4- (p-toluene-sulfamoyl) diphenylamine, Ν'-dimethyl-Ν, Ν'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyi-1-naphthylamine, N- (4-t-octylphenyl) - 1 - naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example, p, p'-di-t-octyldiphenylamine, 4-n-butylaminophenoi, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-

Octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyimethane, Ν, Ν, Ν ', Ν'-tetramethyl- 4,4'-diaminodiphenylmethane, 1, 2-bis [(2-methylphenyl) amino] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3' - dimethylbutyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine. a mixture of mono- and dialkylated t-butyl / t-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated dialkylated t-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated t-butyl / t-octylphenothiazines, a mixture of mono- and dialkylated t Octylo-phenothiazines, N-allylphenothiazine and / or Ν, Ν, Ν ', Ν'-tetraphenyl-1,4-diaminobut-2-ene, preferred is a mixture of mono- and dialkylated t-butyl / t-octyl-diphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated t-butyldiphenylamines. In a preferred embodiment of the present invention, the antioxidant comprises A4.1, which is free of amino groups, containing compounds

i) phenol derivatives,

ii) lactones

iii) phosphorus derivatives,

as well as any mixtures of these compounds, and the antioxidant A4.2 at least one compound with one or more secondary amino groups.

It may further be provided that the antioxidant A4.1 at least one phenol derivative i) and the antioxidant A4.2 at least one compound of the formula

(IR 1 R2 (VII) includes, in the R l C1-C18 alkyl, phenyl-C l -C 4 alkyl. C5-C 1 2-C ^'ycloalkyl. Phenyl. Naphthyl, phenyl or naphthyl each of which is substituted by C1-C12 alkyl or C1-C12 alkoxy or benzyi or α, α-dimethylbenzyl, and R2 phenyl, naphthyl, phenyl or naphthyl, each of which is substituted by C1-C12 alkyl or C1-C12 alkoxy or benzyi or α, α -

Dimethylbenzyl correspond. In a further embodiment, antioxidant A4.1 is used in an amount of 0.02-3.0 parts by weight, preferably 0.04-2.0 parts by weight, particularly preferably 0.05-1.5% by weight Parts, based on the sum of the parts by weight of components AI and A2, and antioxidant A4.2 in an amount of 0.02 3.0 parts by weight, preferably 0.04-2.0 parts by weight. Parts, particularly preferably 0.05 1, 5 parts by weight, based on the sum of parts by weight of components used AI and A2.

In a further embodiment, the erfmdungsgemäße process in the presence of

A4.1 0.02 3.0 parts by weight, preferably 0.04-2.0 parts by weight, particularly preferably 0.05

1.5 parts by weight, based on the sum of the parts by weight of components Al and A2, of at least one compound selected from the group consisting of 2,6-di- (t-butyl) -p-cresol (BHT), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4 -methylphenol, N, N'-l, 6-hexamethylene-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide, alkyl-3- (3,5-di-t-butyl) 4-hydroxyphenylpropionate) wherein alkyl comprises a carbon radical having Cl to C24, preferably Cl to C20, particularly preferably Cl to C18, ethyl en (bisoxyethylene) bis - (3, (5-t-butylhydroxy-4-tolyl) propionate 4,4'-butylidenebis (6-t-butyl-3-methylphenol) and / or tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E),

and

A4.2 0.02-3.0 parts by weight, preferably 0.04-2.0 parts by weight, particularly preferably 0.05

1.5 parts by weight, based on the sum of the parts by weight of components AI and A2, at least one compound selected from the group consisting of N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (l, 4- dimethyloentyl) -p-phenylenediamine, N, ^' - bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, -dicyclohexyl-p phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3 - Dimethylbutyl) - N '-phenyl-p-phenylenediamine, N- (1-methylpyloxy) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine , Ν, Ν'-dimethyl-Ν, Ν'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-t-octylphenyl) 1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-t-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyiaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethyiphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, Ν, Ν, Ν ', Ν' - Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1, 2

Bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated t-butyl Butyl / t-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / Isohexyldiphenylaminen, a mixture of mono- and dialkylated t-butyldiphenylamines, 2,3- Dihydro-3,3-dimethyi-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated t-butyl / t-octylphenothiazines, a mixture of mono- and dialkylated t-octyl-phenothiazines, N-allylphenothiazine and / or Ν, Ν, Ν ', Ν'-tetraphenyl-1, 4-diaminobut-2-ene,.

In a further embodiment, the process according to the invention is carried out in the presence of

A4.1 0.02 3.0 parts by weight, preferably 0.04 ----- 2.0 parts by weight, particularly preferably 0.05 1.5 parts by weight, based on the sum of the wt Parts of components AI and

A2, at least one compound selected from the group consisting of 2,6-di- (t-butyl) -p-cresol (BHT), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] - methane, alkyl 3- (3,5-di-t-butyl-4-hydroxyphenylpropionate), wherein alkyl comprises a carbon radical with Cl to C18, octadecyi-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ), α-tocopherol, β-tocopherol, γ-tocopherol and / or δ-

tocopherol, and

A4.2 0.02 3.0 parts by wt., Preferably 0.04-2.0 parts by wt., Particularly preferably 0.05.

1.5 parts by wt., Based on the sum of the parts by wt. Of components Al and A2, at least one compound selected from the group consisting of mono- and dialkylated t-butyl / tert-octyldiphenylaminen, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyidiphenylamines, a mixture of mono- and dialkylated isopropyl / Isohexyldiphenylaminen, a mixture of mono- and dialkylated t-Butyldiphenylaminen.

Component A5

As component A5, from 0 to 10 parts by weight of auxiliaries and additives are used, in particular from 0.1 to 8.0 parts by weight, preferably from 0.1 to 7.5 parts by weight, more preferably from 0.15 to 7.0 parts by wt., In each case based on the sum of the parts by wt. Of components AI and A2. Suitable auxiliaries and additives in the context of the process according to the invention are, for example, the following components which can be used individually or in any desired combination:

a) catalysts,

b) surface-active additives, such as emulsifiers and foam stabilizers, in particular those with low emission, such as products of the

Tegostab® LF series,

c) additives such as reaction retarders (for example, acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes), pigments, dyes, solid flame retardants (such as melamine and / or

Ammoniumpolypho sphat), liquid flame retardants (eg Halogenhaltigewie example tris (2-Chlorpropy l) pho sphat or halogen-free, eg based on oligomeric phosphates, as described for example in EP 2687534 and US 4382042), further stabilizers against aging and weathering, plasticizers , fungistatic and bacteriostatic substances, fillers

(such as barium sulfate, kieselguhr, carbon black or whiting) and release agents.

These optionally used auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18-21. Further examples of auxiliaries and additives optionally to be used according to the invention as well as details of usage and additives The mode of action of these auxiliaries and additives are described in the Kunststoff-Handbuch, Volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Munich, 3rd edition, 1993, for example on pages 104-127. Preferred catalysts are aliphatic tertiary amines (for example trimethylamine, triethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (for example 1,4-diaza (2,2,2) bicyclooctane), aliphatic aminoethers (for example dimethylaminoethyl ether and N, N, N-trimethyl N-hydroxyethyl bisaminoethyl ether), cycloaliphatic amino ethers

(For example, N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkyl ureas, see, for example, EP-A 0 176 013, in particular (3-dimethylaminopropylamine) urea) and tin catalysts (such as dibutyltin oxide , Dibutyltin dilaurate, tin (II) ethylhexanoate, Zinnricinoleat) used. Component B

Suitable di- and / or polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula (VIII)

Q (NCO) _n , (VIII) in the

n = 2 4, preferably 2 -3,

and

Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 6 to 13 C atoms or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 C, atoms.

These are, for example, those polyisocyanates such as are cited in EP-A 0 007 502, pages 7-8. As a rule, the technically readily available polyisocyanates are preferably used, for example the 2,4- and 2,6-tolylene diisocyanate, as well as any desired mixtures of these isomers ("TDI"); Polyphenylpolymethylenpolyisocyanate, as prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates ("modified polyisocyanates"), in particular such modified polyisocyanates, which differs from Derive 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate. Preferably, one or more compounds selected from the group consisting of 2,4- and 2,6-tolylene diisocyanate, 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and Polyphenylpolymethylenpolyisocyanat ("multi-core MDI ") used.

In a further embodiment of the present invention, the isocyanate component B comprises a toluylene diisocyanate isomer mixture comprising 55 to 90% by weight of 2,4 and 10 to 45% by weight.

2,6-TDI. In a further embodiment of the present invention, the index is> 70 to <130, preferably> 85 to <125, more preferably> 90 to <120. The index (index) indicates the percentage ratio of the actual amount of isocyanate used to stoichiometric, ie for the conversion of OH equivalents calculated amount of isocyanate groups (NCO) - amount of:

Code = [I used amount of cyano]: (calculated amount of isocyanate) · 100 (IX)

The polyurethane foams obtainable according to the invention find, for example, the following application: furniture upholstery, Textileiniagen, mattresses, automobile seats, headrests, armrests, sponges, foam films for use in automotive parts such as headliners, door side panels, Si t / pads and components.

The rigid polyurethane foams and flexible polyurethane foams produced according to the invention typically exhibit lower tendency to discoloration during storage in air and also under the influence of light, in particular UV light.

The present invention will be explained below with reference to exemplary embodiments.

Examples

Used chemicals:

Arcol Poiyoi 1 108: tri functional polyether polyol based on glycerol with Hydro xyzahl 48 mg KOH / g, obtained by copolymerization of 12 wt .-% ethylene oxide with

88% by weight of propylene oxide.

C02 Polyol Type IOC: tri functional polyol based on glycerol with hydroxyl / ahl 50 mg KOH / g, obtained by copolymerization of 20.5% by weight of carbon dioxide with 79.5% by weight of propylene oxide.

Tegostab BF 2370: Siloxane-based foam stabilizer Tegostab ^® BF2370, from Evonik Goldschmidt.

Desmophen 41WB01: tri functional polyol based on glycerol with OHZ 37, obtained by copolymerization of 62 wt .-% EO and 20 wt .-% PO, 83% prim. OH - sip.

Addocat 108E: catalyst bis (2-dimethylamino-ethyl) ether in dipropylene glycol, available as Addocat ^® 108, from Rhein Chemie.. Dabco T-9: Tin (II) -ethylexanoat available as Dabco ^® T-9, Air Products.

Desmodur T80: Mixture of 80 wt .-% 2,4- and 20 wt .-% 2,6-toluene diisocyanate.

methods:

Color angle determination:

The color angle is determined by using a digital camera (Sony DSC-R I) to photograph the respective sample body lying on a white sheet of paper, perform a white balance against the white sheet of paper, and then adjust the hue as the color angle from the HSi. M od eil from the recording using an image analysis software (AnalySIS) is determined. The color tone is determined as color angle H on the color wheel (0 ° = red. 120 ° = green, 240 ° = blue) and specifies the dominant wavelength of the color, except for the range between blue-violet and red (240 ° and 360 °), where he indicates a position on the purple line. This measurement is carried out in each case with a color-stable polyurethane foam produced according to the invention after the aforementioned aging and a reference polystyrene foam aged in the same way carried out. The determined color angles of the color-stable polyurethane foam and of the reference polyurethane foam are subtracted from one another and thus provide the invention by at least 5 ° lower displacement of the color angle in the color-stable polyurethane foam. The measured foams are substantially green in color so that the absolute values of the color angles are on the order of about 120 °.

Polyurethane foams were prepared according to the recipes given in Table 1 below. Listed are the proportions of the components in parts by weight.

The bulk density and compression hardness were determined in accordance with DIN EN ISO 3386-1.

Tensile strength and tensile strength were determined according to DIN EN ISO 1798.

Compression set was determined according to DIN EN ISO 1856.

Table 1: Compositions used From Table 1 it can be seen that tests VI and V3 as well as V2 and V4 each contrast a polyurethane foam according to the invention and a corresponding reference foam. All foams VI to V4 were prepared immediately after each other. After cooling and complete reaction of the foams, rectangular specimens with edge lengths HxWxD of 4 × 10 × 10 cm were cut out. The specimens thus produced were then over a period of 90 days at 20 ° C and 40% rel. Humidity stored in a laboratory under daylight conditions on one of its flat sides. The flat pages are labeled page 1 (top) and page 2 (bottom). Pages 3 to 5 correspond to three side surfaces. The fourth side surface was not measured in each case since the samples were labeled on it. The sample V2 according to the invention was turned at regular intervals from one to the other flat side, so that the two flat sides were exposed to daylight for about the same amount of time. Samples VI, V3 and V4 were not turned. The blank value after storage was determined by cutting the specimens in the center after measuring the outside and determining the color value at the center of the cut surface. Since the center of the specimen was exposed neither to the light nor directly to the air, this value can be used as a comparison of how much the foams have changed color since their preparation. Subsequently, the specimens were subjected to the aforementioned color angle determination. The results are shown in Tables 2 and 3 below and in Figs. 1 and 2 summarized:

Page: VI [°] V2 [°] V3 [°] V4 [°]

1 91, 41 121, 41 85.78 91, 88

2 134.06 121, 41 91, 41 81, 09

3 89.06 88.59 57.19 69.38

4 95.63 93.75 85.78 78.28

5 73.59 83.91 65.16 73.59

Blank value 143.81 150.28 139.09 143.96

Table 2: Results of color angle measurements.

Page V3-V1 [°] V4-V2 [°]

1 -5.63 -29.53

2 -42.66 -40.31

3 -31, 88 -19.22

4 -9.84 -15.47

5 -8.44 -10.31

Table 3: Determination of the shift of the color angle in comparison between the inventive and the comparative samples. For the Faxb angles lower values indicate an increasing color change of the foams, here a yellowing, that is a shift from greenish (120 °) to yellow (90 °) shades. The freshly produced foams have essentially the same greenish starting color, ie they are in the range of about 100 to 120 °.

The results show that the use according to the invention of polyethercarbonate polyols for the production of polyurethane foams leads to a marked improvement in the dyeing stability in comparison to conventional polyurethane foams based only on polyetherpolyols. On each sample surface the Färbwinkelverschiebungsdifferenz to the direct comparison sample is more than 5 °, in part even nearly 43 °. In particular, on the bottom 2 of the sample 1, a significantly lower color shift is observed than in the bottom 2 of the direct comparison sample 3. In the sample 2 shows that the regular turning of the sample body, the top 1 and the bottom 2 a total of lower and also have experienced identical color shift, which is even significantly lower than that of the bottom 2 of the direct comparison sample. 4

Claims

claims

1. Use of a polyol component comprising> 50 to <100 wt .-% based on the Poiyolkomponente of at least one Polyetherearbonatpolyols AI having a hydroxyl value according to DIN 53240 of> 20 mg KOH / g to <300 mg KOH / g to produce color-stable

Polyurethane foam.

Use of a component A for producing color-stable polyurethane containing chaumsto ffe

Al> 50 to <100 parts by weight of at least one Polyetherearbonatpolyols with a

Hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <300 mg KOH / g, A2 <50 to> 0 parts by weight of at least one polyether polyol having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g, where the

Polyetherpoiyol is free of carbonate units,

A3 0.5 to 25 parts by weight, based on the sum of parts by weight of the components

AI and A2, water and / or physical blowing agents,

A5 0 to 10 parts by weight, based on the sum of the parts by weight of components AI and A2, auxiliaries and additives,

wherein all parts by weight of components AI to A5 are normalized so that the sum of parts by weight AI + A2 in the composition 100 results.

Use according to claim 2, characterized in that for the preparation of the color-stable polyurethane foams, the component A with a component B containing

B diisocyanates and / or polyisocyanates,

is reacted at an isocyanate index of 70 to 130.

Use according to claim 2 or 3, characterized in that the component A contains> 55 to <100 parts by weight of the Polyetherearbonatpolyols AI and <45 to> 0 parts by weight of the polyether polyol A2, in particular> 60 to <100 wt. Parts of the Polyetherearbonatpolyols AI and <40 to> 0 parts by weight of the polyether polyol A2.

Use according to one of claims 2 to 4, characterized in that 100 parts by weight

AI, 0 parts by weight of A2 and apart from AI no further organic polyols for

Production of the color-stable polyurethane chaumsto ffe be used.

6. Use according to any one of the preceding claims, characterized in that the polyether carbonate polyol A has a hydroxyl value according to DIN 53240 of> 24 mg KOH / g to <280 mg KOH / g, more preferably from> 40 mg KOH / g to <280 mg KOH /G.

Use according to one of the preceding claims, characterized in that the polyethercarbonate polyol Al has an average OH functionality of 2.3 to 3.5, in particular from 2.5 to 3.3, preferably from 2.7 to 3.1, especially preferably 2.8 to 3.0. 8. Use according to one of the preceding claims, characterized in that the polyethercarbonate polyol Al is obtainable by copolymerization of> 2 wt .-% to <30 wt .-% carbon dioxide and> 70 wt .-% to <98 wt .-% one or more alkylene oxides in the presence of one or more H-functional starter molecules having an average functionality of> 1 to <6, preferably> 1 to <4, more preferably> 2 to <3, wherein the polyether carbonate polyol AI is in particular obtainable under

Use of multimetal cyanide catalysts or double metal cyanide catalysts.

Use according to one of the preceding claims, characterized in that the polyethercarbonate polyol Al is obtainable using ethylene oxide and / or

Propylene oxide, in particular using propylene oxide.

10. Use according to any one of the preceding claims, characterized in that the polyethercarbonate polyol AI has blocks according to formula (I) with a ratio e / f of 2: 1 to 1: 20

in particular from 1, 5: 1 to 1:10.

Use according to one of claims 2 to 10, characterized in that the component A4 as component A4.1 0.02 to 5.0 parts by weight, based on the sum of the parts by weight of components AI and A2, of an antioxidant contains, which is free of amino groups, and as component A4.2 0.02 - 5.0 parts by weight, based on the sum of the parts by weight of components AI and A2, of an antioxidant which at least one compound with a or more amino groups, wherein the total content of the Component A4 is in particular 0.04 to 10.0 parts by weight, based on the sum of the parts by weight of component AI and A2.

12. Use according to claim 11, characterized in that the antioxidant A4.1

i) phenol derivatives,

ii) lactones

iii) phosphorus derivatives

and any mixtures of these compounds,

and the antioxidant A4.2

at least one compound having one or more secondary amino groups.

Use according to one of claims 2 to 12, characterized in that component B is 2,4-, 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'-, 2,2'-diphenylmethane diisocyanate (MDI ) and / or polyphenyl polymethylene polyisocyanate ("multi-core MDI") comprises or consists thereof.

Use according to one of claims 2 to 13, characterized in that the color-stable polyurethane foam in the form of a rectangular or square sample on the center of at least one of its flat sides by at least 5 ° lower displacement of the color angle in the HSI model after storage over a period of 90 days at 20 ° C and 40% rel. Humidity as a reference polyurethane foam, which is prepared and stored in the same manner as the color-stable polyurethane foam, wherein the reference polyurethane foam differs from the color-stable polyurethane chaumsto ff only that for its preparation instead of the polyethercarbonate polyol AI a largely identical amount of Polyetherpolyols without carbonate units but with the same hydroxyl number as far as possible according to DI 53240 is used, the shift of the color angle in the HSI model is in particular at least 8 °, preferably at least 10 °, more preferably at least 15 °.

Use of a stably stable polyurethane foam obtainable according to one of claims 2 to 14 for the production of furniture upholstery, textile inserts, mattresses, automobile seats,

Headrests, armrests, sponges, foam sheets for use in automotive parts such as headliners, door panels, seat cushions, and components.